Catalytic cracking



March 21, 1967 A. G. GoBLE. ETAL CATALYTIC CRACKING Filed June 15. 1962 5M .y c e f s a a a. -000 f ae. f m a 2 .w 0W F 7 .0 w

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oo M M0 -7m 3f am w 4 w -3f/w -f ATTORNEYS United States Patent O 3,310,597 CATALYTIC CRACKING Anthony George Goble and Alan Richard Thornhill, Sunbury-on-Thames, England, assignors to The British Petroleum Company Limited, London, England, a British joint-stock corporation Filed June 13, 1962, Ser. No. 202,277 Claims priority, application Great Britain, June 22, 1961, 22,624/ 61 5 Claims. ,(Cl. 260-683) This invention relates to the catalytic cracking of hydrocarbons to produce, particularly, normally-gaseous olens.

Normally gaseous olens, for example ethylene and propylene, are extensively used as starting materials for the production of a variety of chemical products. They are normally obtained from heavier hydrocarbons, particularly petroleum fractions, by a thermal cracking process. The process may, if desired, be operated in the presence of steam, in which case it is commonly known as steam cracking or in the presence of inert solid particles, for example sand, in which case it is commonly known as sand cracking. Thermal cracking processes suffer, however, from lack of selectivity in the olens produced and with the increasing emphasis on propylene yas a chemical feedstock it is desirable to obtain products with a higher propylenezethylene ratio. Catalytic cracking is also a well known process for t-he production of lower boiling hydrocarbons b-ut the emphasis up to the present lhas been on theprod-uction of normally-liquid products such as gasolines, any normally-gaseous hydrocarbons produced being considered a by-product and kept to a minimum. Y 1

The present invention is concerned with a catalyst cracking process for the production of normally-gaseous olens having a high propylene content and, according to the present invention, normally liquid hydrocarbons are contacted at elevated temperature with a catalyst comprising alumina and combined halogen, the propylenerethylene ratio in the product being greater than unity.

The preferred halogen is uorine and the catalyst may be prepared i'n any convenient manner, for example Vby contacting alumina with a halogen compound containing halogen together with one or more of the elements, carbon, hydrogen or oxygen under conditions such that halogen combines with the alumina.

Details of one suitable method are given in co-pending U.S. patent application Ser. No. 197,850 filed may 28, 1962, now abandoned.

Suitable halogen contents of the catalyst are in the range 0.1 to wt. preferably G25-5% wt. In the complete specification of U.K. Patent No. 956,685 it has been shown that the isomerisation activity of catalysts containing alumina and uorine is more properly related to the amount of tluorine per unit of catalyst surface area than to the total weight of luorine, i.e. the optimum fluorine content for any catalyst depends on its surface area. The samecon'siderations may apply here also since it has been found, for example, that catalysts with the same weight of iluorine but different surface areas have different activities. Preferably the amount of fiuorine per unit of catalyst surface area is 0.25 10-4 to 2.() 104 grams/sq. metre.

The support may. consist essentially of alumina or it ICC may be a mixture containing a Imajor proportion of alumina and a minor proportion of one or more other refractory oxides preferably selected from Groups III to V of the Periodic Table. Any of the so-called activated aluminas normally used as catalyst supports may be used.

In addition to the production of gaseous olens high in propylene content, the liquid product obtained by the process of the invention has increased aromatic content, and by suitable adjustment of process conditions, substantial yields of individual yaromatic hydrocarbons such as benzene, toluene and xylenes can be obtained.

It hasbeen found that for any given contact time, as

the operating temperature is increased the yield .of propylene increases to a maximum and then falls away. This effect is also observed in the yields of individual aromatics obtained. The feedstocks to the present process may be the same as those normally used for the thermal cracking processes, for example naphtha fractions boiling within the range C., to 200 C. or gas-oil fractions boiling wit-hin the range 20G-450 C.

For a given degree of conversion the process of the l present invention operates at a lower temperature than a thermal cracking process, suitable temperatures being for example, within the range 450-800" C. If high propylene yield is the main consideration, particularly suitable temperatures lie within the range 50G-700 C. with contact times preferably within the range 0.05-1.0 sec. If high aromatics production is required, ya rather broader range of temperature may be required, for example within the ange 500-750 C., with a similar range of contact times. Alkyl aromatics are produced at the lower temperatures of this range, dealkylation to benzene taking place to an increasing extent as the temperature rises. Increase of temperature and decrease of contact time thus increase the degree of conversion up to a given point but the propylenezethylene ratio at maximum propylene yield -appears to be constant independent of contact time. Decrease of contact time increases the temperatures required to give the maximum propylene yield and also decreases the paraffinzolen ratio.

The catalyst may be used in any convenient form, for example a uidised or moving bed.

'Ilhe invention is illustrated by the following examples.

Example 1 A catalyst of alumina andcombincd lluorine, having 6.0% wt. of combined uorine was prepared as follows:

A sample of eta-alumina, produced by hydrolysis` of aluminium isopropoxide followed by subsequent calcination, was contacted at 450 C. for 20 minutes wit-h a stream of carbon tetrauoride gas (GF4) flowing at 9() mL/min. Afterwards it was allowed to cool in dry nitro'- gen and stored in a sealed container.

The catalyst was used to crack a light naphtha of Middle'East origin having an ASTM boiling range of 37 to 66.5 C. under a range of process conditions. The experiments were carried out in a microreactor and the products were analysed by gas chromatography. The contact time was calculated as the catalyst volume in millilitres divided by t-he feed hydrocarbon rate in millif litres of vapour per second, corrected for pressure and to a temperature of 800 C. Process conditions and product yields are given in Table 1 below.

TAB LE 1 Sand Cracking Cracking with alumina] fluorine catalyst Equivalent contact time at 800 C sec 0.93 2. 40 0.057 0. 22 0.89 Temperature, C 785 775 670 640 590 Pressure, p si e' 15 5 15 15 15 Product Yields:

Methane, percent wt. on feed 14 18 6 7 5 Ethane, percent wt. on feed. 3 2 5 5 4 Ethylene, percent wt. on icc 23 26 18 20 12 Propane, percent wt. on feed Tr. Tr. 5 8 12 Propylene, percent wt. on feed 17 20 25 25 19 Total Conversion to Cl-Ca Hydrocarbons, percent wt. on feed 57 66 59 65 52 Propylene/ethylene wt. ratio 0. 73 0. 74 1. 42 1. 28 1. 43 Propane/propylene wt. ratio 0. 18 0.32 0. 63

The table shows that, as compared to sand cracking, cracking with an alumina/ liuorine catalyst gives a similar conversion at a much lower temperature with a considerably higher propylenezethylene wt. ratio. It also shows a relatively constant propylenezethylene ratio independent of contact time.

Example 2 A catalyst of alumina and combined fluor-ine, containing 1.24% weight of uorine, was prepared as follows:

20 mls. of commercial eta-alumina was allowed to soak in 100 mls. of a hydrofluoric acid solution prepared by mixing 0.25 ml. of 40% volume hydrofluoric `acid in 100 mls. of water. The catalyst was washed with 100 mls. of water and dried at 120 C.

The catalyst was used to crack a light gas oil, ASTM boiling range 20S-363 C. in a micro-reactor at various temperatures within the range 35 0-65 0 C. but at constant pressure and contact time. The products were analysed by gas chromatography and the maximum yield of propylene was obtained at 515 C.

Process conditions, product yields and comparable figures for sand cracking are given in Table 2 below:

TABLE 2 Cracking Conditions and Yields at Sand with Maximum Propylene Yield Cracking Alumina] Fluorine Catalyst Equivalent contact time at 800 C., sec 0.87 0.87 Temperature, C 750 515 Pressure, p.s.i.g 15

Product Yields:

Methane, percent Wt. on feed 10 2 Ethane, percent wt. on feed... 4 1 Ethylene, percent wt. on feed. 21 8 Propane, percent wt. on fecd (1) 3 Propylene, percent wt. on feed 16 19 Total conversion to Cl-C hydrocarbons,

percent wt. on feed 51 33 Propylcne/ethylene weight ratio 0. 76 2. 4 Propane/propylene weight ratio 0. 11

The table shows that, compared to sand cracking, cracking with the alumina/ fluorine catalyst gives a greater yield of propylene at a much lower temperature and with a much higher propylenezethylene weight ratio.

The effect on aromatic yields is shown in the `accompanying graph, FIG. 1. It is seen that a maximum benzene yield of 11.2% weight is obtained at 775 C. For comparison sand cracking g-ave 5.6% of benzene at 775 C. increasing to 10% at 900 C. A maximum toluene yield of 10.7% weight was obtained at 430 C. compared with 1.6% using sand at the same temperature. A maximum yield of xylene of 10.5% weight was obtained at 535 C. compared with under 2% using sand. Thus larger yields of aromatics are, obtained using aluminauorine catalyst and at lower temperatures than when using sand.

The aromatic yields corresponding to the process conditions shown in Table 2 are given in the following Table Percent weight on feed of Ctr-CB aromatics -Total conversion to Cl-Cg hydrocarbons (percent Weight on feed) 1 Expressed as X 100 The total Cs-C aromatic yield increases with temperature to 850 C. with sand, and to a maximum at 600 C. with the -alumina/fluorine catalyst. The yields at these temperatures are shown in the following Table 4:

TABLE 4 Cracking Sand with Cracking Alumina] Fluorine Catalyst Temperature, C 850 600 Product Yields:

Benzene, percent wt. on feed 9. 2 4. 3 Toluene, percent wt. on feed-. 2. 9 9.8 Xylenes, percent wt. on feed 5.8

Total C-C aromatics, percent wt. on

feed 12. 1 19.9

Example 3 The feedstock of Example 1 was contacted with the catalyst of Example 1 at various contact times in a microreactor, the temperatures being increased in each case.

The effect on propylene yield is shown in the accompanying graph FIG. 2. It is seen that the propylene yield rises to la peak in each case, the shorter the contact time the higher the peak and the higher .the temperature required to attain the peak.

Example 4 The feedstock of Example 2 was treated at 615 C. and 15 p.s.i.g. in a micro-reactor with a ser-ies of catalysts'- cornprising predominantly eta-alumina having a surface area of 193 m2. per gram and containing varying quantiJ ties -of uorine, the contact time in each case being 0.8 second. The pnopylene yield in each case was determined by gas chromatography. The effect of uorine content is illustrated in the accompanying graph, FIG. 3.

We claim:

1. A process comprising contacting a normally liquid hydrocarbon feedstock, which is a petroleum distillate boiling in the range C4-450" C., at an elevated temperature in the range of 450800 C., with a catalyst consist- 4ing essentially of alumina, in a major proportion, and combined uorine in an amount of 0.1 to 15% by weight of the catalyst, the amount of uorine per unit of catalyst surface area being 0.25X10-4 to 2.0 104 g./sq. meter; and, recovering a product containing normally gaseous oletins, the propylene:ethylene weight ratio in the product being greater than unity.

2. A process as claimed in claim 1 wherein the catalyst contains between 025-5 weight of halogen.

peraturre is in the range 5 00-75 0 C.

4. A process as claimed in claim 1 wherein the temperature is in the range SOO-700 C.

5. A process as claimed in claim 1 wherein the contact time is within -the range 0.05-1.0 second.

References Cited by the Examiner UNITED STATES PATENTS 2,479,110 8/ 1949 Haensel 208-139 2,848,380 8/1958 Thomas 252-441 X 2,859,174 11/1958 Adams et al 208-115 2,937,213 5/1960 Hutchings et al. 260-683 2,951,883 9/ 1960 Kroeper et a1 260-683 3,121,696 2/1964 Hoekstra 252-441 3,138,559 6/1964 Haupt-Schein et al. 252-441 X DELBERT E. GANTZ, Primary Examiner.

ALPHONSO D. SULLIVAN, Examiner.

2() C. E. SPRESSER, JR., Assistant Examiner. 

1. A PROCESS COMPRISING CONTACTING A NORMALLY LIQUID HYDROCARBON FEEDSTOCK, WHICH IS A PETROLEUM DISTILLATE BOILING IN THE RANGE C4-450*C., AT AN ELEVATED TEMPERATURE IN THE RANGE OF 450-800*C., WITH A CATALYST CONSISTING ESSENTIALLY OF ALUMINA, IN A MAJOR PROPORTION, AND COMBINED FLUORINE IN AN AMOUNT OF 0.1 TO 15% BY WEIGHT OF THE CATALYST, THE AMOUNT OF FLUORINE PER UNIT OF CATALYST SURFACE AREA BEING 0.25X10**-4 TO 2.0X10**-4 G./SQ. METER; AND, RECOVERING A PRODUCT CONTAINING NORMALLY GASEOUS OLEFINS, THE PROPYLENE:ETHYLENE WEIGHT RATIO IN THE PRODUCT BEING GREATER THAN UNITY. 